JP7049888B2 - Organic electroluminescence elements, display devices, lighting devices - Google Patents
Organic electroluminescence elements, display devices, lighting devices Download PDFInfo
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- JP7049888B2 JP7049888B2 JP2018064868A JP2018064868A JP7049888B2 JP 7049888 B2 JP7049888 B2 JP 7049888B2 JP 2018064868 A JP2018064868 A JP 2018064868A JP 2018064868 A JP2018064868 A JP 2018064868A JP 7049888 B2 JP7049888 B2 JP 7049888B2
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- 238000005401 electroluminescence Methods 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 120
- 229910044991 metal oxide Inorganic materials 0.000 claims description 37
- 150000004706 metal oxides Chemical class 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 34
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 150000007514 bases Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 171
- 238000002347 injection Methods 0.000 description 77
- 239000007924 injection Substances 0.000 description 77
- 239000000463 material Substances 0.000 description 40
- -1 2, 3-Dihydrobenzo [d] thiazole compound Chemical class 0.000 description 34
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 33
- 125000004432 carbon atom Chemical group C* 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- 230000005525 hole transport Effects 0.000 description 18
- 239000011787 zinc oxide Substances 0.000 description 16
- 239000000370 acceptor Substances 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 238000004770 highest occupied molecular orbital Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 8
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- 238000004776 molecular orbital Methods 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 229920000265 Polyparaphenylene Polymers 0.000 description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
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- 238000007740 vapor deposition Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical class N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 5
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- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N 3-methoxypyridine Chemical compound COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
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- 229910052791 calcium Inorganic materials 0.000 description 4
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- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
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- 229910000449 hafnium oxide Inorganic materials 0.000 description 4
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- NKVDKFWRVDHWGC-UHFFFAOYSA-N iridium(3+);1-phenylisoquinoline Chemical compound [Ir+3].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 NKVDKFWRVDHWGC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical compound N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- MKZHJJQCUIZEDE-UHFFFAOYSA-N 1-[(2-hydroxy-3-naphthalen-1-yloxypropyl)-propan-2-ylamino]-3-naphthalen-1-yloxypropan-2-ol Chemical compound C1=CC=C2C(OCC(O)CN(CC(O)COC=3C4=CC=CC=C4C=CC=3)C(C)C)=CC=CC2=C1 MKZHJJQCUIZEDE-UHFFFAOYSA-N 0.000 description 3
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical class COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 3
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical class C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 3
- XQABVLBGNWBWIV-UHFFFAOYSA-N 4-methoxypyridine Chemical compound COC1=CC=NC=C1 XQABVLBGNWBWIV-UHFFFAOYSA-N 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
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- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical compound C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 description 2
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- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical class C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 2
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
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- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
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- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 2
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
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- 239000010931 gold Substances 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
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- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 1
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Description
本発明は、有機エレクトロルミネッセンス（以下、エレクトロルミネッセンス（電界発光）を「ＥＬ」とも記す。）素子、表示装置、照明装置に関する。 The present invention relates to an organic electroluminescence (hereinafter, electroluminescence (electroluminescence) is also referred to as "EL") element, a display device, and a lighting device.
有機ＥＬ素子は、薄く、柔軟でフレキシブルである。有機ＥＬ素子を用いた表示装置は、現在主流となっている液晶表示装置およびプラズマ表示装置と比べて、高輝度、高精細な表示が可能である。また、有機ＥＬ素子を用いた表示装置は、液晶表示装置に比べて視野角が広い。そのため、有機ＥＬ素子を用いた表示装置は、テレビや携帯電話のディスプレイ等としての利用の拡大が期待されている。有機ＥＬ素子は、照明装置への利用も期待されている。 The organic EL element is thin, flexible and flexible. A display device using an organic EL element is capable of high-luminance and high-definition display as compared with the liquid crystal display device and the plasma display device which are currently mainstream. Further, the display device using the organic EL element has a wider viewing angle than the liquid crystal display device. Therefore, display devices using organic EL elements are expected to be widely used as displays for televisions and mobile phones. Organic EL elements are also expected to be used in lighting devices.
有機ＥＬ素子は、陰極と陽極との間に、電子輸送層、発光層、正孔輸送層等の複数の層が積層された構造を有する。有機ＥＬ素子の構造は、基板側から陽極、発光層等の複数の層、陰極がこの順に積層される順構造と、基板側から陽極、発光層等の複数の層、陰極がこの順に積層される逆構造とに分けられる。 The organic EL element has a structure in which a plurality of layers such as an electron transport layer, a light emitting layer, and a hole transport layer are laminated between a cathode and an anode. The structure of the organic EL element consists of a sequential structure in which a plurality of layers such as an anode and a light emitting layer and a cathode are laminated in this order from the substrate side, and a plurality of layers such as an anode and a light emitting layer and a cathode are laminated in this order from the substrate side. It can be divided into the reverse structure.
逆構造の有機ＥＬ素子としては、有機ＥＬ素子を構成する層の一部が無機物からなる有機無機ハイブリッド型の有機ＥＬ素子（Ｈｙｂｒｉｄ Ｏｒｇａｎｉｃ Ｉｎｏｒｇａｎｉｃ ＬＥＤ：ＨＯＩＬＥＤ）が報告されている。このハイブリッド型素子では電子注入層に無機酸化物を用いており、アルカリ金属を用いずに電子注入が可能であるため、通常の有機ＥＬ素子に比べて酸素及び水分に対する耐性に優れている。
逆構造の有機ＥＬ素子では、基板上に発光層を形成する前に電子注入層を形成する。したがって、例えば、スパッタ法を用いて無機酸化物等で電子注入層を形成しても、発光層が損傷を受けることがなく、ハイブリッド型の素子作製に有利である。
As an organic EL element having a reverse structure, an organic-inorganic hybrid type organic EL element (Hybrid Organic Organic LED: HOILED) in which a part of the layer constituting the organic EL element is made of an inorganic substance has been reported. In this hybrid type element, an inorganic oxide is used for the electron injection layer, and electrons can be injected without using an alkali metal. Therefore, the resistance to oxygen and water is superior to that of a normal organic EL element.
In the organic EL element having the reverse structure, the electron injection layer is formed before the light emitting layer is formed on the substrate. Therefore, for example, even if the electron injection layer is formed of an inorganic oxide or the like by a sputtering method, the light emitting layer is not damaged, which is advantageous for manufacturing a hybrid type device.
逆構造の有機ＥＬ素子の無機酸化物層は電子注入層として機能するが（例えば、非特許文献１－５参照。）、無機酸化物層は有機層への電子注入性が不充分である。
そのため、無機酸化物層の上に、さらに電子注入層を成膜することにより、有機ＥＬ素子の電子注入性を改善する技術がある。例えば、非特許文献６には、高分子電解質からなる電子注入層を有する有機ＥＬ素子が記載されている。非特許文献７には、アミンが電子の注入速度の改善に有効であることが記載されている。非特許文献８～１１には、電極と有機層との界面における、アミノ基が電子注入に及ぼす効果について記載されている。
The inorganic oxide layer of the organic EL element having the reverse structure functions as an electron injection layer (see, for example, Non-Patent Document 1-5), but the inorganic oxide layer has insufficient electron injection property into the organic layer.
Therefore, there is a technique for improving the electron injection property of an organic EL device by further forming an electron injection layer on the inorganic oxide layer. For example, Non-Patent
しかし、非特許文献６～１１のような電子注入層を有する逆構造の有機ＥＬ素子では、陽極からの正孔の注入に比べて陰極からの電子の注入が遅いため、陽極から注入される正孔により電子注入層界面で材料が劣化し、素子の駆動安定性が乏しくなる。
However, in an organic EL device having an inverted structure having an electron injection layer as in
本発明は、前記事情に鑑みてなされたものであり、駆動安定性に優れた逆構造の有機ＥＬ素子、および前記有機ＥＬ素子を用いた表示装置、照明装置を提供することを課題とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic EL element having an inverted structure having excellent drive stability, and a display device and a lighting device using the organic EL element.
本発明者は、逆構造の有機ＥＬ素子の駆動安定性を高めることができる材料について種々検討したところ、特定のドナー性の基と特定のアクセプター性の基とを組み合わせた化合物が、正孔に対して安定であることを見出した。そして、この化合物を逆構造の有機ＥＬ素子の材料として用いると、素子の駆動安定性を高められることを見出し、本発明に想到した。 The present inventor has investigated various materials capable of enhancing the driving stability of an organic EL device having an inverted structure, and found that a compound combining a specific donor group and a specific acceptor group is converted into a hole. On the other hand, it was found to be stable. Then, they have found that when this compound is used as a material for an organic EL device having a reverse structure, the drive stability of the device can be improved, and the present invention has been conceived.
本発明は、以下の構成を有する。
［１］基板上に、陰極と発光層と陽極とがこの順に設けられた有機ＥＬ素子であって、前記陰極と前記発光層の間に、下記式（ａ）で示される環構造を含む基と下記式（ｂ）で示される環構造を含む基とを有する化合物を含む層を有することを特徴とする、有機ＥＬ素子。
The present invention has the following configurations.
[1] An organic EL device in which a cathode, a light emitting layer, and an anode are provided in this order on a substrate, and a group including a ring structure represented by the following formula (a) between the cathode and the light emitting layer. An organic EL device comprising a layer containing a compound having a group having a ring structure represented by the following formula (b).
（ただし、式（ａ）中の－＊１は、前記化合物中の式（ａ）で示される環構造を含む基以外の原子と結合する結合子である。式（ｂ）中の－＊２は、前記化合物中の式（ｂ）で示される環構造を含む基以外の原子と結合する結合子である。）
［２］前記層が、還元剤をさらに含む、［１］に記載の有機ＥＬ素子。
［３］前記層が、酸解離定数ｐＫａが１以上である塩基性の化合物をさらに含む、［１］又は［２］に記載の有機ＥＬ素子。
［４］前記層と前記陰極との間に金属酸化物層を有する、［１］～［３］のいずれかに記載の有機ＥＬ素子。
［５］［１］～［４］のいずれかに記載の有機ＥＬ素子を含むことを特徴とする表示装置。
［６］［１］～［４］のいずれかに記載の有機ＥＬ素子を含むことを特徴とする照明装置。
(However, − * 1 in the formula (a) is a binder that bonds to an atom other than the group containing the ring structure represented by the formula (a) in the compound. − * 2 in the formula (b). Is a bonder that binds to an atom other than the group containing the ring structure represented by the formula (b) in the compound.)
[2] The organic EL device according to [1], wherein the layer further contains a reducing agent.
[3] The organic EL element according to [1] or [2], wherein the layer further contains a basic compound having an acid dissociation constant pKa of 1 or more.
[4] The organic EL device according to any one of [1] to [3], which has a metal oxide layer between the layer and the cathode.
[5] A display device comprising the organic EL element according to any one of [1] to [4].
[6] A lighting device comprising the organic EL element according to any one of [1] to [4].
本発明の有機ＥＬ素子は、逆構造で、駆動安定性が優れている。本発明の表示装置、照明装置は、用いる逆構造の有機ＥＬ素子の駆動安定性が優れている。 The organic EL element of the present invention has an inverted structure and is excellent in drive stability. The display device and the lighting device of the present invention have excellent drive stability of the organic EL element having the reverse structure used.
＜有機ＥＬ素子＞
本発明の有機ＥＬ素子は、基板上に陰極と発光層と陽極とがこの順に設けられ、陰極と発光層の間に、後述の式（ａ）で示される環構造を含む基と、後述の式（ｂ）で示される環構造を含む基とを有する化合物（以下、「化合物（１）」とも記す。）を含む層を有する。陰極と発光層の間に形成される化合物（１）を含む層は、電子注入輸送層となる。
<Organic EL element>
In the organic EL device of the present invention, a cathode, a light emitting layer, and an anode are provided on a substrate in this order, and a group containing a ring structure represented by the formula (a) described later between the cathode and the light emitting layer, and a group described later. It has a layer containing a compound having a group having a ring structure represented by the formula (b) (hereinafter, also referred to as “compound (1)”). The layer containing the compound (1) formed between the cathode and the light emitting layer is an electron injection transport layer.
本発明の有機ＥＬ素子の構造は、基板、陰極、化合物（１）を含む電子注入輸送層、発光層、陽極を有する逆構造であればよい。基板、陰極、化合物（１）を含む電子注入輸送層、発光層、陽極以外の層としては、正孔輸送層、正孔注入層、金属酸化物層等が挙げられ、適宜選択できる。 The structure of the organic EL element of the present invention may be an inverse structure having a substrate, a cathode, an electron injection transport layer containing the compound (1), a light emitting layer, and an anode. Examples of the substrate, the cathode, the electron injection transport layer containing the compound (1), the light emitting layer, and the layer other than the anode include a hole transport layer, a hole injection layer, a metal oxide layer, and the like, which can be appropriately selected.
本発明の有機ＥＬ素子としては、例えば、図１に例示した有機ＥＬ素子１、図２に例示した有機ＥＬ素子１Ａが挙げられる。なお、図１、図２の寸法等は一例であって、本発明はそれらに必ずしも限定されるものではなく、その要旨を変更しない範囲で適宜変更して実施することが可能である。
Examples of the organic EL element of the present invention include the
有機ＥＬ素子１は、基板２上に、陰極３と、金属酸化物層４と、電子注入輸送層５と、発光層６と、正孔輸送層７と、正孔注入層８と、陽極９とがこの順に設けられた積層構造を有する。
有機ＥＬ素子１Ａは、基板２上に、陰極３と、電子注入輸送層５と、発光層６と、正孔輸送層７と、正孔注入層８と、陽極９とがこの順に設けられた積層構造を有する。
The
The
本発明の有機ＥＬ素子の積層構造は、有機ＥＬ素子１，１Ａのような積層構造が好ましい。また、有機ＥＬ素子１のように、陰極と、化合物（１）を含む電子注入輸送層の間に、金属酸化物層を有することがより好ましい。金属酸化物層を有する有機ＥＬ素子は、金属酸化物層を有しない有機ＥＬ素子に比べて、連続駆動寿命や保存安定性に優れる。
As the laminated structure of the organic EL element of the present invention, a laminated structure such as the
（電子注入輸送層）
電子注入輸送層は、化合物（１）を含む層である。電子注入輸送層に含まれる化合物（１）は、１種でもよく、２種以上でもよい。
化合物（１）は、下記式（ａ）で示される環構造（以下、「環構造ａ」とも記す。）を含む基と、下記式（ｂ）で示される環構造（以下、「環構造ｂ」とも記す。）を含む基とを有する化合物である。すなわち、化合物（１）は、環構造ａ（カルバゾール環）を含む骨格と環構造ｂ（トリアジン環）を含む骨格とを有する化合物である。化合物（１）は、環構造ａを含む基がドナー性を示し、環構造ｂを含む基がアクセプター性を示す。
(Electron injection transport layer)
The electron injection transport layer is a layer containing compound (1). The compound (1) contained in the electron injection transport layer may be one kind or two or more kinds.
The compound (1) has a group containing a ring structure represented by the following formula (a) (hereinafter, also referred to as “ring structure a”) and a ring structure represented by the following formula (b) (hereinafter, “ring structure b”). It is a compound having a group containing). That is, the compound (1) is a compound having a skeleton containing a ring structure a (carbazole ring) and a skeleton containing a ring structure b (triazine ring). In compound (1), the group containing the ring structure a exhibits donor property, and the group containing ring structure b exhibits acceptor property.
ただし、式（ａ）中の－＊１は、化合物（１）中の環構造ａを含む基以外の原子と結合する結合子である。式（ｂ）中の－＊２は、化合物（１）中の環構造ｂを含む基以外の原子と結合する結合子である。 However, − * 1 in the formula (a) is a bonder that binds to an atom other than the group containing the ring structure a in the compound (1). -* 2 in the formula (b) is a bond that binds to an atom other than the group containing the ring structure b in the compound (1).
環構造ａを含む基は、環構造ａを独立の環構造として有していてもよく、環構造ａを含むより大きな環構造として有していてもよい。環構造ａを含むπ共役系のより大きな環構造としては、インドロカルバゾール環、ベンゾフランカルバゾール環等が挙げられる。 The group containing the ring structure a may have the ring structure a as an independent ring structure or may have a larger ring structure including the ring structure a. Examples of the larger ring structure of the π-conjugated system including the ring structure a include an indrocarbazole ring and a benzofurancarbazole ring.
環構造ａを含む基としては、例えば、下式（ａ１）～（ａ４）で示される基が挙げられる。 Examples of the group containing the ring structure a include the groups represented by the following formulas (a1) to (a4).
式（ａ１）中のＸ１は、１つまたは２つが下記式（１ａ－１）～（１ａ－５）で示される基であり、残りがそれぞれ独立に水素原子、または、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、炭素数１～１０のアルキルアミノ基、炭素数２～１０のアシル基、炭素数７～２０のアラルキル基、置換もしくは未置換の炭素数６～３０の芳香族炭化水素基、および、置換もしくは未置換の炭素数３～３０の芳香族複素環基からなる群から選択される置換基である。
式（ａ２）中のＸ２は、それぞれ独立に水素原子、または、下記式（１ａ－１）～（１ａ－５）で示される基、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、炭素数１～１０のアルキルアミノ基、炭素数２～１０のアシル基、炭素数７～２０のアラルキル基、置換もしくは未置換の炭素数６～３０の芳香族炭化水素基、および、置換もしくは未置換の炭素数３～３０の芳香族複素環基からなる群から選択される置換基である。
Ｒは、水素原子、芳香族炭化水素基または芳香族複素環基である。
式（ａ３）中のＸ３、式（ａ４）中のＸ４は、それぞれ式（ａ２）中のＸ２と同じである。
One or two of X 1 in the formula (a1) are groups represented by the following formulas (1a-1) to (1a-5), and the rest are independently hydrogen atoms or 1 to 10 carbon atoms, respectively. Alkyl group, alkoxy group with 1 to 10 carbon atoms, alkylthio group with 1 to 10 carbon atoms, alkylamino group with 1 to 10 carbon atoms, acyl group with 2 to 10 carbon atoms, aralkyl group with 7 to 20 carbon atoms, It is a substituent selected from the group consisting of a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms and a substituted or unsubstituted aromatic heterocyclic group having 3 to 30 carbon atoms.
X 2 in the formula (a2) is an independently hydrogen atom, a group represented by the following formulas (1a-1) to (1a-5), an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Alkoxy group, alkylthio group with 1 to 10 carbon atoms, alkylamino group with 1 to 10 carbon atoms, acyl group with 2 to 10 carbon atoms, aralkyl group with 7 to 20 carbon atoms, substituted or unsubstituted 6 to 10 carbon atoms. It is a substituent selected from the group consisting of 30 aromatic hydrocarbon groups and substituted or unsubstituted aromatic heterocyclic groups having 3 to 30 carbon atoms.
R is a hydrogen atom, an aromatic hydrocarbon group or an aromatic heterocyclic group.
X3 in the formula ( a3 ) and X4 in the formula (a4) are the same as X2 in the formula ( a2 ), respectively.
式（１ａ－１）～（１ａ－５）中のＲ１は、それぞれ独立に水素原子、または、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基、炭素数１～１０のアルキルチオ基、炭素数１～１０のアルキルアミノ基、炭素数２～１０のアシル基、炭素数７～２０のアラルキル基、置換もしくは未置換の炭素数６～３０の芳香族炭化水素基、および、置換もしくは未置換の炭素数３～３０の芳香族複素環基からなる群から選択される置換基であり、隣り合う置換基は一体となって環を形成していてもよい。
－＊３は、Ｘ１～Ｘ４が結合している環の炭素原子と結合する結合子を示す。
R 1 in the formulas (1a-1) to (1a-5) is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms, respectively. Alkylthio groups, alkylamino groups with 1 to 10 carbon atoms, acyl groups with 2 to 10 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups with 6 to 30 carbon atoms, and It is a substituent selected from the group consisting of substituted or unsubstituted aromatic heterocyclic groups having 3 to 30 carbon atoms, and the adjacent substituents may form a ring together.
-* 3 indicates a bond that bonds to the carbon atom of the ring to which X 1 to X 4 are bonded.
以下、式（ａ１）で示される基を「基（ａ１）」と記し、他の式で示される基も同様に記す。
基（ａ１）が２つの基（１ａ－１）～（１ａ－５）を有する場合、それら２つの基は、Ｘ１が結合している環構造中の別のベンゼン環にそれぞれ結合していることが好ましい。
基（ａ１）中の基（１ａ－１）～（１ａ－５）でないＸ１としては、化合物（１）の合成の容易性の観点から、水素原子が好ましい。
Hereinafter, the group represented by the formula (a1) will be referred to as “group (a1)”, and the groups represented by other formulas will be described in the same manner.
When the group (a1) has two groups (1a-1) to (1a-5), the two groups are each bonded to another benzene ring in the ring structure to which X 1 is bonded. Is preferable.
As X1 which is not a group (1a- 1 ) to (1a-5) in the group (a1), a hydrogen atom is preferable from the viewpoint of easiness of synthesizing the compound (1).
基（ａ２）が基（１ａ－１）～（１ａ－５）を有する場合、基（１ａ－１）～（１ａ－５）の数は、１つまたは２つが好ましい。基（ａ２）中の２つの基（１ａ－１）～（１ａ－５）を有する場合、それら２つの基は、Ｘ２が結合している環構造中の別のベンゼン環にそれぞれ結合していることが好ましい。
基（ａ２）中のＸ２としては、化合物（１）の合成の容易性の観点から、水素原子が好ましい。
基（ａ２）中のＲとしては、芳香族炭化水素基が好ましく、フェニル基がより好ましい。
When the group (a2) has groups (1a-1) to (1a-5), the number of groups (1a-1) to (1a-5) is preferably one or two. When having two groups (1a-1) to (1a-5) in the group (a2), the two groups are respectively bonded to another benzene ring in the ring structure to which X2 is bonded. It is preferable to have.
As X2 in the group ( a2 ), a hydrogen atom is preferable from the viewpoint of easiness of synthesizing the compound (1).
As R in the group (a2), an aromatic hydrocarbon group is preferable, and a phenyl group is more preferable.
基（ａ３）が基（１ａ－１）～（１ａ－５）を有する場合、基（１ａ－１）～（１ａ－５）の数は、１つまたは２つが好ましい。基（ａ３）中の２つの基（１ａ－１）～（１ａ－５）を有する場合、それら２つの基は、Ｘ３が結合している環構造中の別のベンゼン環にそれぞれ結合していることが好ましい。
基（ａ３）中のＸ３としては、化合物（１）の合成の容易性の観点から、水素原子が好ましい。
When the group (a3) has groups (1a-1) to (1a-5), the number of groups (1a-1) to (1a-5) is preferably one or two. When having two groups (1a-1) to (1a-5) in the group (a3), the two groups are respectively bonded to another benzene ring in the ring structure to which X3 is bonded. It is preferable to have.
As X3 in the group ( a3), a hydrogen atom is preferable from the viewpoint of easiness of synthesizing the compound (1).
基（ａ４）が基（１ａ－１）～（１ａ－５）を有する場合、基（１ａ－１）～（１ａ－５）の数は、１つまたは２つが好ましい。基（ａ４）中の２つの基（１ａ－１）～（１ａ－５）を有する場合、それら２つの基は、Ｘ４が結合している環構造中の別のベンゼン環にそれぞれ結合していることが好ましい。
基（ａ４）中のＸ４としては、化合物（１）の合成の容易性の観点から、水素原子が好ましい。
When the group (a4) has groups (1a-1) to (1a-5), the number of groups (1a-1) to (1a-5) is preferably one or two. When having two groups (1a-1) to (1a-5) in the group (a4), the two groups are respectively bonded to another benzene ring in the ring structure to which X4 is bonded. It is preferable to have.
As X4 in the group ( a4), a hydrogen atom is preferable from the viewpoint of easiness of synthesizing the compound (1).
基（１ａ－１）～（１ａ－５）のようなカルバゾール基はすべてドナー性に寄与し、また結合位置によらず同等のドナー性を示す。
基（１ａ－１）～（１ａ－５）中のＲ１としては、化合物（１）の合成の容易性の観点から、水素原子が好ましい。
All carbazole groups such as the groups (1a-1) to (1a-5) contribute to the donor property and show the same donor property regardless of the binding position.
As R1 in the groups (1a-1) to (1a-5), a hydrogen atom is preferable from the viewpoint of easiness of synthesizing the compound (1).
環構造ｂを含む基は、環構造ｂを独立の環構造として有していてもよく、環構造ｂを含むより大きな環構造として有してもよい。
環構造ｂを含む基としては、例えば、下記の基（ｂ１）～（ｂ３）が挙げられる。
The group containing the ring structure b may have the ring structure b as an independent ring structure or may have a larger ring structure including the ring structure b.
Examples of the group containing the ring structure b include the following groups (b1) to (b3).
ただし、式（ｂ１）、（ｂ２）中のＡｒ１は、それぞれ独立に芳香族炭化水素基または芳香族複素環基を示す。 However, Ar 1 in the formulas (b1) and (b2) independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group, respectively.
Ａｒ１としては、フェニル基が好ましい。
環構造ｂを含む基としては、基（ｂ１）が好ましく、Ａｒ１がフェニル基である基（ｂ１）がより好ましい。
As Ar 1 , a phenyl group is preferable.
As the group containing the ring structure b, the group (b1) is preferable, and the group (b1) in which Ar 1 is a phenyl group is more preferable.
化合物（１）としては、環構造ａを含む基と環構造ｂを含む基とが直接的に結合している化合物であってもよく、環構造ａを含む基と環構造ｂを含む基とが間接的に結合している化合物であってもよい。
環構造ａを含む基と環構造ｂを含む基とが間接的に結合している化合物としては、環構造ａを含む基と環構造ｂを含む基がそれぞれベンゼン環に置換されている化合物が好ましく、環構造ａを含む基と環構造ｂを含む基がそれぞれベンゼン環のオルト位に置換されている化合物がより好ましい。
The compound (1) may be a compound in which a group containing a ring structure a and a group containing a ring structure b are directly bonded to each other, and a group containing the ring structure a and a group containing the ring structure b. May be a compound indirectly bound to.
Examples of the compound in which the group containing the ring structure a and the group containing the ring structure b are indirectly bonded include a compound in which the group containing the ring structure a and the group containing the ring structure b are each substituted with a benzene ring. More preferably, a compound in which the group containing the ring structure a and the group containing the ring structure b are substituted at the ortho positions of the benzene ring is more preferable.
化合物（１）の具体例としては、例えば、下記式（１－１）～（１－１０）で示される化合物が挙げられる。
以下、式（１－１）で示される化合物を「化合物（１－１）」とも記し、他の式で示される化合物も同様に記す。
Specific examples of the compound (1) include compounds represented by the following formulas (1-1) to (1-10).
Hereinafter, the compound represented by the formula (1-1) is also referred to as “compound (1-1)”, and the compounds represented by other formulas are also referred to in the same manner.
化合物（１）を含む電子注入輸送層は、化合物（１）に加えてさらに他の材料を含んでもよい。
電子注入輸送層は、還元剤をさらに含むことが好ましい。還元剤は、ｎ－ドーパントとして働く。電子注入輸送層が還元剤を含む場合、陰極から発光層への電子の供給が充分に行われやすく、有機ＥＬ素子の発光効率がより一層向上する。
The electron injection transport layer containing the compound (1) may contain other materials in addition to the compound (1).
The electron injection transport layer preferably further contains a reducing agent. The reducing agent acts as an n-dopant. When the electron injection transport layer contains a reducing agent, electrons are easily supplied from the cathode to the light emitting layer, and the luminous efficiency of the organic EL element is further improved.
還元剤としては、電子供与性の化合物であれば特に制限されない。還元剤の具体例としては、例えば、１，３－ジメチル－２，３－ジヒドロ－１Ｈ－ベンゾ［ｄ］イミダゾール、１，３－ジメチル－２－フェニル－２，３－ジヒドロ－１Ｈ－ベンゾ［ｄ］イミダゾール、（４－（１，３－ジメチル－２，３－ジヒドロ－１Ｈ－ベンゾイミダゾール－２－イル）フェニル）ジメチルアミン（Ｎ－ＤＭＢＩ）、１，３，５－トリメチル－２－フェニル－２，３－ジヒドロ－１Ｈ－ベンゾ［ｄ］イミダゾール等の２，３－ジヒドロベンゾ［ｄ］イミダゾール化合物；３－メチル－２－フェニル－２，３－ジヒドロベンゾ［ｄ］チアゾール等の２，３－ジヒドロベンゾ［ｄ］チアゾール化合物；３－メチル－２－フェニル－２，３－ジヒドロベンゾ［ｄ］オキサゾール等の２，３－ジヒドロベンゾ［ｄ］オキサゾール化合物；ロイコクリスタルバイオレット（＝トリス（４－ジメチルアミノフェニル）メタン）、ロイコマラカイトグリーン（＝ビス（４－ジメチルアミノフェニル）フェニルメタン）、トリフェニルメタン等のトリフェニルメタン化合物；２，６－ジメチル－１，４－ジヒドロピリジン－３，５－ジカルボン酸ジエチル（ハンチュエステル）等のジヒドロピリジン化合物等が挙げられる。電子注入輸送層に含まれる還元剤は、１種でもよく、２種以上でもよい。
還元剤としては、２，３－ジヒドロベンゾ［ｄ］イミダゾール化合物や、ジヒドロピリジン化合物が好ましく、Ｎ－ＤＭＢＩまたは２，６－ジメチル－１，４－ジヒドロピリジン－３，５－ジカルボン酸ジエチル（ハンチュエステル）がより好ましい。
The reducing agent is not particularly limited as long as it is an electron-donating compound. Specific examples of the reducing agent include, for example, 1,3-dimethyl-2,3-dihydro-1H-benzo [d] imidazole, 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo [d]. d] Imidazole, (4- (1,3-dimethyl-2,3-dihydro-1H-benzoimidazol-2-yl) phenyl) dimethylamine (N-DMBI), 1,3,5-trimethyl-2-phenyl -2,3-Dihydro-1H-benzo [d] imidazole and other 2,3-dihydrobenzo [d] imidazole compounds; 3-methyl-2-phenyl-2,3-dihydrobenzo [d] thiazole and the like 2, 3-Dihydrobenzo [d] thiazole compound; 2,3-dihydrobenzo [d] oxazol compound such as 3-methyl-2-phenyl-2,3-dihydrobenzo [d] oxazole; leucocrystal violet (= tris (4) -Triphenylmethane compounds such as (dimethylaminophenyl) methane), leucomarakite green (= bis (4-dimethylaminophenyl) phenylmethane), triphenylmethane; 2,6-dimethyl-1,4-dihydropyridine-3,5 -Dihydropyridine compounds such as diethyl dicarboxylic acid (Huntuester) and the like can be mentioned. The reducing agent contained in the electron injection transport layer may be one kind or two or more kinds.
As the reducing agent, 2,3-dihydrobenzo [d] imidazole compound and dihydropyridine compound are preferable, and N-DMBI or 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid diethyl (hanchu ester) is preferable. Is more preferable.
電子注入輸送層に還元剤が含まれる場合、電子注入輸送層中の還元剤の含有量は、電子注入輸送層中の化合物（１）１００質量部に対して、０．１～１５質量部が好ましく、０．５～１０質量部がより好ましく、１～５質量部がさらに好ましい。還元剤の含有量が前記範囲内であれば、有機ＥＬ素子の発光効率がより一層高くなる。 When the electron injection transport layer contains a reducing agent, the content of the reducing agent in the electron injection transport layer is 0.1 to 15 parts by mass with respect to 100 parts by mass of the compound (1) in the electron injection transport layer. Preferably, 0.5 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. When the content of the reducing agent is within the above range, the luminous efficiency of the organic EL element is further increased.
電子注入輸送層は、酸解離定数ｐＫａが１以上の塩基性の化合物（以下、「塩基性化合物Ａ」とも記す。）をさらに含むことが好ましい。なお、「ｐＫａ」は「水中における酸解離定数」を意味する。塩基性化合物Ａは、化合物（１）からプロトン（Ｈ＋）を引き抜く能力を有する。そのため、電子注入輸送層が塩基性化合物Ａを含むことで電子注入性がより一層向上する。 The electron injection transport layer preferably further contains a basic compound having an acid dissociation constant pKa of 1 or more (hereinafter, also referred to as “basic compound A”). In addition, "pKa" means "acid dissociation constant in water". Basic compound A has the ability to extract protons (H + ) from compound (1). Therefore, when the electron injection transport layer contains the basic compound A, the electron injection property is further improved.
塩基性化合物ＡのｐＫａは、１以上であり、５以上が好ましく、１１以上がより好ましい。塩基性化合物Ａは、ｐＫａが高い化合物であるほど、化合物（１）からプロトンを引き抜く能力がより高いものとなる。 The pKa of the basic compound A is 1 or more, preferably 5 or more, and more preferably 11 or more. The higher the pKa of the basic compound A, the higher the ability to extract protons from the compound (1).
塩基性化合物Ａとしては、３級アミン誘導体、メトキシピリジン誘導体、ジアザビシクロノネン誘導体、ジアザビシクロウンデセン誘導体、フォスファゼン塩基誘導体、グアニジン環状誘導体等が挙げられる。電子注入輸送層に含まれる塩基性化合物Ａは、１種でもよく、２種以上でもよい。 Examples of the basic compound A include a tertiary amine derivative, a methoxypyridine derivative, a diazabicyclononene derivative, a diazabicycloundecene derivative, a phosphazene base derivative, a guanidine cyclic derivative and the like. The basic compound A contained in the electron injection transport layer may be one kind or two or more kinds.
３級アミン誘導体としては、４－ジメチルアミノピリジン（４－ＤＭＡＰ）、２－ジメチルアミノピリジン（２－ＤＭＡＰ）、トリエチルアミン等が挙げられる。３級アミン誘導体としては、より長寿命を得る観点から、４－ＤＭＡＰが好ましい。
メトキシピリジン誘導体としては、４－メトキシピリジン（４－ＭｅＯＰ）、３－メトキシピリジン（３－ＭｅＯＰ）等が挙げられる。メトキシピリジン誘導体としては、ｐＫａが高いため、４－ＭｅＯＰが好ましい。
Examples of the tertiary amine derivative include 4-dimethylaminopyridine (4-DMAP), 2-dimethylaminopyridine (2-DMAP), triethylamine and the like. As the tertiary amine derivative, 4-DMAP is preferable from the viewpoint of obtaining a longer life.
Examples of the methoxypyridine derivative include 4-methoxypyridine (4-MeOP) and 3-methoxypyridine (3-MeOP). As the methoxypyridine derivative, 4-MeOP is preferable because pKa is high.
ジアザビシクロノネン誘導体としては、１，５－ジアザビシクロ［４．３．０］ノネン－５（ＤＢＮ）等が挙げられる。ジアザビシクロノネン誘導体としては、より長寿命を得る観点から、ＤＢＮが好ましい。
ジアザビシクロウンデセン誘導体としては、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）等が挙げられる。
Examples of the diazabicyclononene derivative include 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and the like. As the diazabicyclononene derivative, DBN is preferable from the viewpoint of obtaining a longer life.
Examples of the diazabicycloundecene derivative include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and the like.
フォスファゼン塩基誘導体としては、１－ｔｅｒｔ－ブチル－２，２，４，４，４－ペンタキス（ジメチルアミノ）－２λ５，４λ５－カテナジ（フォスファゼン）（Ｐｈｏｓｐｈａｚｅｎｅ ｂａｓｅ Ｐ２－ｔ－Ｂｕ）等が挙げられる。
グアニジン環状誘導体としては、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン（ＭＴＢＤ）、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン（ＴＢＤ）等が挙げられる。
Examples of the phosphazene base derivative include 1-tert-butyl-2,2,4,4,4-pentakis (dimethylamino) -2λ5,4λ5 - catenadi (phosphazene) (Phosphazene base P2-t-Bu) and the like. Be done.
Examples of the guanidine cyclic derivative include 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene (MTBD) and 1,5,7-triazabicyclo [4.4.0]. ] Deca-5-en (TBD) and the like can be mentioned.
還元剤および塩基性化合物Ａ以外の他の材料を用いてもよく、例えば、トリス－１，３，５－（３’－（ピリジン－３’’－イル）フェニル）ベンゼン（ＴｍＰｙＰｈＢ）のようなピリジン誘導体、（２－（３－（９－カルバゾリル）フェニル）キノリン（ｍＣＱ））のようなキノリン誘導体、２－フェニル－４，６－ビス（３，５－ジピリジルフェニル）ピリミジン（ＢＰｙＰＰＭ）のようなピリミジン誘導体、ピラジン誘導体、バソフェナントロリン（ＢＰｈｅｎ）のようなフェナントロリン誘導体、２，４－ビス（４－ビフェニル）－６－（４’－（２－ピリジニル）－４－ビフェニル）－［１，３，５］トリアジン（ＭＰＴ）のようなトリアジン誘導体、３－フェニル－４－（１’－ナフチル）－５－フェニル－１，２，４－トリアゾール（ＴＡＺ）のようなトリアゾール誘導体、オキサゾール誘導体、２－（４－ビフェニリル）－５－（４－ｔｅｒｔ－ブチルフェニル－１，３，４－オキサジアゾール）（ＰＢＤ）のようなオキサジアゾール誘導体、２，２’，２’’－（１，３，５－ベントリイル）－トリス（１－フェニル－１－Ｈ－ベンズイミダゾール）（ＴＰＢＩ）のようなイミダゾール誘導体、ナフタレン、ペリレン等の芳香環テトラカルボン酸無水物、ビス［２－（２－ヒドロキシフェニル）ベンゾチアゾラト］亜鉛（Ｚｎ（ＢＴＺ）２）、トリス（８－ヒドロキシキノリナト）アルミニウム（Ａｌｑ３）等に代表される各種金属錯体、２，５－ビス（６’－（２’，２’’－ビピリジル））－１，１－ジメチル－３，４－ジフェニルシロール（ＰｙＰｙＳＰｙＰｙ）等のシロール誘導体に代表される有機シラン誘導体等が挙げられる。 Materials other than the reducing agent and the basic compound A may be used, such as Tris-1,3,5- (3'-(pyridine-3''-yl) phenyl) benzene (TmPyPhB). Like pyridine derivatives, quinoline derivatives such as (2- (3- (9-carbazolyl) phenyl) quinoline (mCQ)), 2-phenyl-4,6-bis (3,5-dipyridylphenyl) pyrimidin (BPyPPM). Pyrimidine derivatives, pyrazine derivatives, phenanthroline derivatives such as vasophenantroline (BPhen), 2,4-bis (4-biphenyl) -6- (4'-(2-pyridinyl) -4-biphenyl)-[1,3 , 5] Triazine derivatives such as triazine (MPT), triazole derivatives such as 3-phenyl-4- (1'-naphthyl) -5-phenyl-1,2,4-triazole (TAZ), oxazole derivatives, 2 Oxaziazole derivatives such as-(4-biphenylyl) -5- (4-tert-butylphenyl-1,3,4-oxadiazole) (PBD), 2,2', 2''-(1, Imidazole derivatives such as 3,5-ventryyl) -tris (1-phenyl-1-H-benzimidazole) (TPBI), aromatic ring tetracarboxylic acid anhydrides such as naphthalene and perylene, bis [2- (2-hydroxy). Phenyl) benzothiazolato] Various metal complexes typified by zinc (Zn (BTZ) 2), tris (8-hydroxyquinolinato) aluminum (Alq3), etc., 2,5-bis (6'-(2', 2'') -Examples include organic silane derivatives typified by syrol derivatives such as -1,1-dimethyl-3,4-diphenylsilol (PyPySPyPy))).
電子注入輸送層の平均厚さは、５～１００ｎｍが好ましく、１０～６０ｎｍがより好ましく、１０～３０ｎｍがさらに好ましい。電子注入輸送層の平均厚さが前記範囲の下限値以上であれば、正孔をブロックする効果が充分に得られやすく、有機ＥＬ素子の駆動安定性がより優れる。電子注入輸送層の平均厚さが前記範囲の上限値以下であれば、駆動電圧を充分に低くしやすい。電子注入輸送層の平均厚さが１０～３０ｎｍの範囲であれば、有機ＥＬ素子の連続駆動寿命が特に長くなる。
電子注入輸送層の平均厚さは、触針式段差計、分光エリプソメトリーにより測定できる。
The average thickness of the electron injection transport layer is preferably 5 to 100 nm, more preferably 10 to 60 nm, still more preferably 10 to 30 nm. When the average thickness of the electron injection transport layer is at least the lower limit of the above range, the effect of blocking holes can be sufficiently obtained, and the driving stability of the organic EL element is more excellent. When the average thickness of the electron injection transport layer is not more than the upper limit of the above range, the drive voltage can be easily lowered sufficiently. When the average thickness of the electron injection transport layer is in the range of 10 to 30 nm, the continuous drive life of the organic EL device becomes particularly long.
The average thickness of the electron injection transport layer can be measured by a stylus type step meter and spectroscopic ellipsometry.
（基板）
基板の材料としては、樹脂材料、ガラス材料等が挙げられる。基板の材料は、１種のみであってもよく、２種以上であってもよい。基板の材料としては、柔軟性に優れた有機ＥＬ素子が得られる観点から、樹脂材料が好ましい。
(substrate)
Examples of the substrate material include a resin material and a glass material. The material of the substrate may be only one kind or two or more kinds. As the material of the substrate, a resin material is preferable from the viewpoint of obtaining an organic EL element having excellent flexibility.
基板に用いられる樹脂材料としては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリアリレート等が挙げられる。
基板に用いられるガラス材料としては、石英ガラス、ソーダガラス、パイレックス（登録商標）等が挙げられる。
Examples of the resin material used for the substrate include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate and the like.
Examples of the glass material used for the substrate include quartz glass, soda glass, Pyrex (registered trademark) and the like.
ボトムエミッション型の有機ＥＬ素子の場合には、基板として透明基板を用いる。トップエミッション型の有機ＥＬ素子の場合は、透明基板を用いてもよく、不透明基板を用いてもよい。
不透明基板としては、アルミナ等のセラミックス材料からなる基板、ステンレス鋼のような金属板の表面に酸化膜（絶縁膜）を形成した基板、樹脂材料で構成された基板等が挙げられる。
In the case of a bottom emission type organic EL element, a transparent substrate is used as the substrate. In the case of a top emission type organic EL element, a transparent substrate may be used or an opaque substrate may be used.
Examples of the opaque substrate include a substrate made of a ceramic material such as alumina, a substrate having an oxide film (insulating film) formed on the surface of a metal plate such as stainless steel, and a substrate made of a resin material.
（陽極及び陰極）
陽極及び陰極としては、公知の導電性材料を適宜用いることができる。陽極及び陰極は、光の取り出しのために少なくともいずれか一方は透明であることが好ましい。
透明導電性材料としては、錫ドープ酸化インジウム（ＩＴＯ）、アンチモンドープ酸化インジウム（ＡＴＯ）、インジウムドープ酸化亜鉛（ＩＺＯ）、アルミニウムドープ酸化亜鉛（ＡＺＯ）、フッ素ドープ酸化インジウム（ＦＴＯ）等が挙げられる。
不透明な導電性材料としては、カルシウム、マグネシウム、アルミニウム、錫、インジウム、銅、銀、金、白金や、これらの合金等が挙げられる。
(Anode and cathode)
As the anode and the cathode, known conductive materials can be appropriately used. It is preferable that at least one of the anode and the cathode is transparent for light extraction.
Examples of the transparent conductive material include tin-doped indium oxide (ITO), antimony-doped indium oxide (ATO), indium-doped zinc oxide (IZO), aluminum-doped zinc oxide (AZO), fluorine-doped indium oxide (FTO), and the like. ..
Examples of the opaque conductive material include calcium, magnesium, aluminum, tin, indium, copper, silver, gold, platinum, and alloys thereof.
陰極の材料としては、ＩＴＯ、ＩＺＯ、ＦＴＯが好ましい。
陽極の材料としては、金、銀、アルミニウムが好ましい。
一般に電極材料として用いられる金属や金属酸化物は陽極にも陰極にも使用でき、上部電極から光を取り出すトップエミッション構造の場合は、例えば、下部電極（陰極）にＡｌ、上部電極（陽極）にＩＴＯ等を使用できる。
As the cathode material, ITO, IZO, and FTO are preferable.
As the material of the anode, gold, silver and aluminum are preferable.
Metals and metal oxides generally used as electrode materials can be used for both the anode and the cathode. In the case of a top emission structure that extracts light from the upper electrode, for example, Al is used for the lower electrode (cathode) and Al is used for the upper electrode (anode). ITO and the like can be used.
陰極の平均厚さは、１０～５００ｎｍが好ましく、１００～２００ｎｍがより好ましい。陰極の平均厚さは、触針式段差計、分光エリプソメトリーにより測定できる。
陽極の平均厚さは、１０～１０００ｎｍが好ましく、３０～１５０ｎｍがより好ましい。なお、不透明な導電性材料を用いる場合でも、例えば平均厚さを１０～３０ｎｍ程度にすることで、トップエミッション型及び透明型の陽極として使用できる。
陽極の平均厚さは、水晶振動子膜厚計により成膜時に測定できる。
The average thickness of the cathode is preferably 10 to 500 nm, more preferably 100 to 200 nm. The average thickness of the cathode can be measured by a stylus type step meter and spectroscopic ellipsometry.
The average thickness of the anode is preferably 10 to 1000 nm, more preferably 30 to 150 nm. Even when an opaque conductive material is used, it can be used as a top emission type or transparent type anode by setting the average thickness to about 10 to 30 nm, for example.
The average thickness of the anode can be measured at the time of film formation with a crystal oscillator film thickness meter.
（金属酸化物層）
金属酸化物層は、陰極の一部または電子注入層として機能する層である。
金属酸化物層としては、１種の金属酸化物膜からなる単層、１種の金属酸化物膜が積層された複層、２種以上の金属酸化物膜が積層された複層、２種以上の金属酸化物が混合された金属酸化物膜を含む単層または複層から選ばれる、半導体膜もしくは絶縁体膜の層である。
(Metal oxide layer)
The metal oxide layer is a layer that functions as a part of the cathode or an electron injection layer.
As the metal oxide layer, there are two types: a single layer composed of one type of metal oxide film, a multi-layer in which one type of metal oxide film is laminated, and a multi-layer in which two or more types of metal oxide films are laminated. It is a layer of a semiconductor film or an insulator film selected from a single layer or a plurality of layers including a metal oxide film mixed with the above metal oxides.
なお、本発明においては、シート抵抗が１００Ω／□より低いものは導電体、シート抵抗が１００Ω／□より高いものは半導体または絶縁体として分類する。電極材料として例示したＩＴＯ、ＡＴＯ、ＩＺＯ、ＡＺＯ、ＦＴＯ等は、導電性が高く半導体または絶縁体の範疇に含まれず、金属酸化物層を構成する金属酸化物には該当しない。 In the present invention, those having a sheet resistance lower than 100Ω / □ are classified as conductors, and those having a sheet resistance higher than 100Ω / □ are classified as semiconductors or insulators. ITO, ATO, IZO, AZO, FTO and the like exemplified as electrode materials have high conductivity and are not included in the category of semiconductors or insulators, and do not correspond to metal oxides constituting the metal oxide layer.
金属酸化物層に用いる金属酸化物を構成する金属元素としては、マグネシウム、カルシウム、ストロンチウム、バリウム、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、インジウム、ガリウム、鉄、コバルト、ニッケル、銅、亜鉛、カドミウム、アルミニウム、ケイ素等が挙げられる。なかでも、マグネシウム、アルミニウム、カルシウム、ジルコニウム、ハフニウム、ケイ素、チタン、亜鉛からなる群から選ばれる金属元素が好ましい。
２種以上の金属酸化物を用いる場合、少なくとも１つの金属酸化物の金属元素は、マグネシウム、アルミニウム、カルシウム、ジルコニウム、ハフニウム、ケイ素、チタン、亜鉛からなる群から選ばれる金属元素が好ましい。
The metal elements that make up the metal oxide used in the metal oxide layer include magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, indium, gallium, and iron. , Cobalt, nickel, copper, zinc, cadmium, aluminum, silicon and the like. Among them, a metal element selected from the group consisting of magnesium, aluminum, calcium, zirconium, hafnium, silicon, titanium and zinc is preferable.
When two or more kinds of metal oxides are used, the metal element of at least one metal oxide is preferably a metal element selected from the group consisting of magnesium, aluminum, calcium, zirconium, hafnium, silicon, titanium and zinc.
金属酸化物層に用いる金属酸化物としては、酸化マグネシウム、酸化アルミニウム、酸化ジルコニウム、酸化ハフニウム、酸化ケイ素、酸化チタン、および酸化亜鉛から選ばれる金属酸化物が好ましい。 As the metal oxide used for the metal oxide layer, a metal oxide selected from magnesium oxide, aluminum oxide, zirconium oxide, hafnium oxide, silicon oxide, titanium oxide, and zinc oxide is preferable.
金属酸化物層に２種以上の金属酸化物を用いる場合、金属酸化物の組み合わせとしては、以下の組み合わせが挙げられる。以下、酸化チタンと酸化亜鉛の組み合わせを「酸化チタン／酸化亜鉛」と記し、その他の組み合わせも同様に記す。
金属酸化物の組み合わせとしては、例えば、酸化チタン／酸化亜鉛、酸化チタン／酸化マグネシウム、酸化チタン／酸化ジルコニウム、酸化チタン／酸化アルミニウム、酸化チタン／酸化ハフニウム、酸化チタン／酸化ケイ素、酸化亜鉛／酸化マグネシウム、酸化亜鉛／酸化ジルコニウム、酸化亜鉛／酸化ハフニウム、酸化亜鉛／酸化ケイ素、酸化カルシウム／酸化アルミニウム等の２種の組み合わせ、酸化チタン／酸化亜鉛／酸化マグネシウム、酸化チタン／酸化亜鉛／酸化ジルコニウム、酸化チタン／酸化亜鉛／酸化アルミニウム、酸化チタン／酸化亜鉛／酸化ハフニウム、酸化チタン／酸化亜鉛／酸化ケイ素、酸化インジウム／酸化ガリウム／酸化亜鉛等の３種の組み合せが挙げられる。
金属酸化物層には、特殊な組成として良好な特性を示す酸化物半導体であるＩＧＺＯや、エレクトライドである１２ＣａＯ７Ａｌ２Ｏ３を用いてもよい。
When two or more kinds of metal oxides are used for the metal oxide layer, the following combinations can be mentioned as the combination of the metal oxides. Hereinafter, the combination of titanium oxide and zinc oxide will be referred to as "titanium oxide / zinc oxide", and other combinations will be described in the same manner.
Examples of the combination of metal oxides include titanium oxide / zinc oxide, titanium oxide / magnesium oxide, titanium oxide / zirconium oxide, titanium oxide / aluminum oxide, titanium oxide / hafnium oxide, titanium oxide / silicon oxide, and zinc oxide / oxidation. Two combinations of magnesium, zinc oxide / zirconium oxide, zinc oxide / hafnium oxide, zinc oxide / silicon oxide, calcium oxide / aluminum oxide, titanium oxide / zinc oxide / magnesium oxide, titanium oxide / zinc oxide / zirconium oxide, There are three combinations such as titanium oxide / zinc oxide / aluminum oxide, titanium oxide / zinc oxide / hafnium oxide, titanium oxide / zinc oxide / silicon oxide, and indium oxide / gallium oxide / zinc oxide.
As the metal oxide layer, IGZO, which is an oxide semiconductor exhibiting good properties as a special composition, or 12CaO 7 Al 2 O 3 , which is an electride, may be used.
金属酸化物層の平均厚さは、１ｎｍから数μｍ程度まで許容できるが、より低電圧で駆動できる有機ＥＬ素子とする観点から、１～１０００ｎｍが好ましく、２～１００ｎｍがより好ましい。
金属酸化物層の平均厚さは、触針式段差計、分光エリプソメトリーにより測定できる。
The average thickness of the metal oxide layer is acceptable from 1 nm to several μm, but is preferably 1 to 1000 nm, more preferably 2 to 100 nm, from the viewpoint of making an organic EL element that can be driven at a lower voltage.
The average thickness of the metal oxide layer can be measured by a stylus type step meter and spectroscopic ellipsometry.
（発光層）
発光層を形成する材料としては、低分子化合物であってもよく、高分子化合物であってもよく、これらを混合して用いてもよい。なお、本発明において低分子材料とは、高分子材料（重合体）ではない材料を意味し、分子量が低い有機化合物を必ずしも意味するものではない。
(Light emitting layer)
The material for forming the light emitting layer may be a low molecular weight compound, a high molecular weight compound, or a mixture thereof. In the present invention, the small molecule material means a material that is not a polymer material (polymer), and does not necessarily mean an organic compound having a low molecular weight.
発光層を形成する高分子材料としては、例えば、トランス型ポリアセチレン、シス型ポリアセチレン、ポリ（ジ－フェニルアセチレン）（ＰＤＰＡ）、ポリ（アルキル，フェニルアセチレン）（ＰＡＰＡ）のようなポリアセチレン系化合物；ポリ（パラ－フェンビニレン）（ＰＰＶ）、ポリ（２，５－ジアルコキシ－パラ－フェニレンビニレン）（ＲＯ－ＰＰＶ）、シアノ－置換－ポリ（パラ－フェンビニレン）（ＣＮ－ＰＰＶ）、ポリ（２－ジメチルオクチルシリル－パラ－フェニレンビニレン）（ＤＭＯＳ－ＰＰＶ）、ポリ（２－メトキシ，５－（２’－エチルヘキソキシ）－パラ－フェニレンビニレン）（ＭＥＨ－ＰＰＶ）のようなポリパラフェニレンビニレン系化合物；ポリ（３－アルキルチオフェン）（ＰＡＴ）、ポリ（オキシプロピレン）トリオール（ＰＯＰＴ）のようなポリチオフェン系化合物；ポリ（９，９－ジアルキルフルオレン）（ＰＤＡＦ）、ポリ（ジオクチルフルオレン－アルト－ベンゾチアジアゾール）（Ｆ８ＢＴ）、α，ω－ビス［Ｎ，Ｎ’－ジ（メチルフェニル）アミノフェニル］－ポリ［９，９－ビス（２－エチルヘキシル）フルオレン－２，７－ジル］（ＰＦ２／６ａｍ４）、ポリ（９，９－ジオクチル－２，７－ジビニレンフルオレニル－オルト－コ（アントラセン－９，１０－ジイル）のようなポリフルオレン系化合物；ポリ（パラ－フェニレン）（ＰＰＰ）、ポリ（１，５－ジアルコキシ－パラ－フェニレン）（ＲＯ－ＰＰＰ）のようなポリパラフェニレン系化合物；ポリ（Ｎ－ビニルカルバゾール）（ＰＶＫ）のようなポリカルバゾール系化合物；ポリ（メチルフェニルシラン）（ＰＭＰＳ）、ポリ（ナフチルフェニルシラン）（ＰＮＰＳ）、ポリ（ビフェニリルフェニルシラン）（ＰＢＰＳ）のようなポリシラン系化合物；さらには特開２０１１－１８４４３０号公報、特開２０１２－１５１１４８号公報に記載のホウ素化合物系高分子材料等が挙げられる。 Examples of the polymer material forming the light emitting layer include polyacetylene compounds such as trans-type polyacetylene, cis-type polyacetylene, poly (di-phenylacetylene) (PDPA), and poly (alkyl, phenylacetylene) (PAPA); poly. (Para-phenylene) (PPV), poly (2,5-dialkoxy-para-phenylene vinylene) (RO-PPV), cyano-substituted-poly (para-phenylene) (CN-PPV), poly (2) -Polyparaphenylene vinylene compounds such as dimethyloctylsilyl-para-phenylene vinylene) (DMOS-PPV), poly (2-methoxy, 5- (2'-ethylhexoxy) -para-phenylene vinylene) (MEH-PPV). Polythiophene compounds such as poly (3-alkylthiophene) (PAT), poly (oxypropylene) triol (POPT); poly (9,9-dialkylfluorene) (PDAF), poly (dioctylfluorene-alto-benzothiazol). ) (F8BT), α, ω-bis [N, N'-di (methylphenyl) aminophenyl] -poly [9,9-bis (2-ethylhexyl) fluoren-2,7-zil] (PF2 / 6am4) , Poly (9,9-dioctyl-2,7-dibinylene fluorenyl-ortho-co (anthracene-9,10-diyl)) polyfluorene compounds; poly (para-phenylene) (PPP), poly Polyparaphenylene compounds such as (1,5-dialkoxy-para-phenylene) (RO-PPP); polycarbazole compounds such as poly (N-vinylcarbazole) (PVK); poly (methylphenylsilane). Polysilane compounds such as (PMPS), poly (naphthylphenylsilane) (PNPS), poly (biphenylenephenylsilane) (PBPS); further described in JP2011-184430A and JP2012-151148. Examples thereof include boron compound-based polymer materials.
発光層を形成する低分子材料としては、トリス（８－ヒドロキシキノリナト）アルミニウム（Ａｌｑ３）、トリス（４－メチル－８キノリノレート）アルミニウム（III）（Ａｌｍｑ３）、８－ヒドロキシキノリン 亜鉛（Ｚｎｑ２）、（１，１０－フェナントロリン）－トリス－（４，４，４－トリフルオロ－１－（２－チエニル）－ブタン－１，３－ジオネート）ユーロピウム（III）（Ｅｕ（ＴＴＡ）３（ｐｈｅｎ））、２，３，７，８，１２，１３，１７，１８－オクタエチル－２１Ｈ，２３Ｈ－ポルフィン プラチナム（II）のような各種金属錯体；ジスチリルベンゼン（ＤＳＢ）、ジアミノジスチリルベンゼン（ＤＡＤＳＢ）のようなベンゼン系化合物、ナフタレン、ナイルレッドのようなナフタレン系化合物、フェナントレンのようなフェナントレン系化合物、クリセン、６－ニトロクリセンのようなクリセン系化合物、ペリレン、Ｎ，Ｎ’－ビス（２，５－ジ－ｔ－ブチルフェニル）－３，４，９，１０－ペリレン－ジ－カルボキシイミド（ＢＰＰＣ）のようなペリレン系化合物、コロネンのようなコロネン系化合物、アントラセン、ビススチリルアントラセンのようなアントラセン系化合物、ピレンのようなピレン系化合物、４－（ジ－シアノメチレン）－２－メチル－６－（パラ－ジメチルアミノスチリル）－４Ｈ－ピラン（ＤＣＭ）のようなピラン系化合物、アクリジンのようなアクリジン系化合物、スチルベンのようなスチルベン系化合物、４，４’－ビス［９－ジカルバゾリル］－２，２’－ビフェニル（ＣＢＰ）、４、４’－ビス（９－エチルー３－カルバゾビニレン）－１，１’－ビフェニル（ＢＣｚＶＢｉ）のようなカルバゾール系化合物、２，５－ジベンゾオキサゾールチオフェンのようなチオフェン系化合物、ベンゾオキサゾールのようなベンゾオキサゾール系化合物、ベンゾイミダゾールのようなベンゾイミダゾール系化合物、２，２’－（パラ－フェニレンジビニレン）－ビスベンゾチアゾールのようなベンゾチアゾール系化合物、ビスチリル（１，４－ジフェニル－１，３－ブタジエン）、テトラフェニルブタジエンのようなブタジエン系化合物、ナフタルイミドのようなナフタルイミド系化合物、クマリンのようなクマリン系化合物、ペリノンのようなペリノン系化合物、オキサジアゾールのようなオキサジアゾール系化合物、アルダジン系化合物、１，２，３，４，５－ペンタフェニル－１，３－シクロペンタジエン（ＰＰＣＰ）のようなシクロペンタジエン系化合物、キナクリドン、キナクリドンレッドのようなキナクリドン系化合物、ピロロピリジン、チアジアゾロピリジンのようなピリジン系化合物、２，２’，７，７’－テトラフェニル－９，９’－スピロビフルオレンのようなスピロ化合物、フタロシアニン（Ｈ２Ｐｃ）、銅フタロシアニンのような金属または無金属のフタロシアニン系化合物、さらには特開２００９－１５５３２５号公報および特許第５６６０３７１号公報に記載のホウ素化合物材料等が挙げられる。これらは、１種または２種以上を用いることができる。
また、量子ドットやペロブスカイト材料も発光層に使用できる。
Examples of the low molecular weight material forming the light emitting layer include tris (8-hydroxyquinolinato) aluminum (Alq3), tris (4-methyl-8 quinolinolate) aluminum (III) (Almq3), 8-hydroxyquinolin zinc (Znq2), and the like. (1,10-Phenantroline) -Tris- (4,4,4-trifluoro-1- (2-thienyl) -butane-1,3-geonate) Europium (III) (Eu (TTA) 3 (phen)) , 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-Various metal complexes such as porphin platinum (II); of distyrylbenzene (DSB), diaminodistyrylbenzene (DADSB). Benzene compounds such as benzene compounds, naphthalene compounds such as naphthalene, naphthalene compounds such as Nile Red, phenanthrene compounds such as phenanthrene, chrysene compounds such as chrysen, 6-nitrochrysen, perylene, N, N'-bis (2,5). -Di-t-butylphenyl) -3,4,9,10-Perylene-di-carboxyimide (BPPC) -based perylene-based compounds, coronene-based compounds such as coronene, anthracene, anthracene such as bisstyrylanthracene Phylogen compounds, pyrene compounds such as pyrene, pyrane compounds such as 4- (di-cyanomethylene) -2-methyl-6- (para-dimethylaminostyryl) -4H-pyran (DCM), such as acridin Aclysin compounds, Stilben compounds such as Stilben, 4,4'-bis [9-dicarbazolyl] -2,2'-biphenyl (CBP), 4,4'-bis (9-ethyl-3-carbazovinylene)- Carbazole compounds such as 1,1'-biphenyl (BCzVBi), thiophene compounds such as 2,5-dibenzoxazolethiophene, benzoxazole compounds such as benzoxazole, benzoimidazole compounds such as benzoimidazole, 2,2'-(para-phenylenedivinylene) -benzothiazole-based compounds such as bisbenzothiazole, bistylyl (1,4-diphenyl-1,3-butadiene), butadiene-based compounds such as tetraphenylbutadiene, na Naphthalimide-based compounds such as phthalimide, coumarin-based compounds such as coumarin, perinone-based compounds such as perinone, oxadiazole-based compounds such as oxadiazole, aldazine-based compounds, 1, 2, 3, 4, Cyclopentadiene compounds such as 5-pentaphenyl-1,3-cyclopentadiene (PPCP), quinacridone compounds such as quinacridone and quinacridone red, pyridine compounds such as pyrolopyridine and thiathiazolopyridine, 2,2 ', 7,7'-Tetraphenyl-9,9'-Spiro compounds such as spirobifluorene, metal or non-metal phthalocyanine compounds such as phthalocyanine (H 2 Pc), copper phthalocyanine, and further, JP-A-2009. Examples thereof include the boron compound materials described in Japanese Patent Publication No. 155325 and Japanese Patent No. 5660371. These can be used alone or in combination of two or more.
Quantum dots and perovskite materials can also be used for the light emitting layer.
（正孔輸送層）
正孔輸送層の材料としては、正孔輸送層の材料として通常用いられているいずれの化合物も用いることができ、各種ｐ型の高分子材料や、各種ｐ型の低分子材料を単独または組み合わせて用いることができる。
(Hole transport layer)
As the material of the hole transport layer, any compound usually used as the material of the hole transport layer can be used, and various p-type polymer materials and various p-type small molecule materials can be used alone or in combination. Can be used.
ｐ型の高分子材料（有機ポリマー）としては、ポリアリールアミン、フルオレン－アリールアミン共重合体、フルオレン－ビチオフェン共重合体、ポリ（Ｎ－ビニルカルバゾール）、ポリビニルピレン、ポリビニルアントラセン、ポリチオフェン、ポリアルキルチオフェン、ポリヘキシルチオフェン、ポリ（ｐ－フェニレンビニレン）、ポリチニレンビニレン、ピレンホルムアルデヒド樹脂、エチルカルバゾールホルムアルデヒド樹脂またはその誘導体等が挙げられる。
これらの化合物は、他の化合物との混合物として用いることもできる。一例として、ポリチオフェンを含有する混合物としては、ポリ（３，４－エチレンジオキシチオフェン／スチレンスルホン酸）（ＰＥＤＯＴ／ＰＳＳ）等が挙げられる。
Examples of the p-type polymer material (organic polymer) include polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer, poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, and polyalkyl. Examples thereof include thiophene, polyhexylthiophene, poly (p-phenylene vinylene), polytinylene vinylene, pyrene formaldehyde resin, ethylcarbazole formaldehyde resin or a derivative thereof.
These compounds can also be used as a mixture with other compounds. As an example, examples of the mixture containing polythiophene include poly (3,4-ethylenedioxythiophene / styrenesulfonic acid) (PEDOT / PSS) and the like.
ｐ型の低分子材料としては、１，１－ビス（４－ジ－パラ－トリアミノフェニル）シクロへキサン、１，１’－ビス（４－ジ－パラ－トリルアミノフェニル）－４－フェニル－シクロヘキサンのようなアリールシクロアルカン系化合物、４，４’，４’’－トリメチルトリフェニルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラフェニル－１，１’－ビフェニル－４，４’－ジアミン、Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ビス（３－メチルフェニル）－１，１’－ビフェニル－４，４’－ジアミン（ＴＰＤ１）、Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ビス（４－メトキシフェニル）－１，１’－ビフェニル－４，４’－ジアミン（ＴＰＤ２）、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラキス（４－メトキシフェニル）－１，１’－ビフェニル－４，４’－ジアミン（ＴＰＤ３）、Ｎ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニル－１，１’－ビフェニル－４，４’－ジアミン（α－ＮＰＤ）、ＴＰＴＥのようなアリールアミン系化合物、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラフェニル－パラ－フェニレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラ（パラ－トリル）－パラ－フェニレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラ（メタ－トリル）－メタ－フェニレンジアミン（ＰＤＡ）のようなフェニレンジアミン系化合物、カルバゾール、Ｎ－イソプロピルカルバゾール、Ｎ－フェニルカルバゾールのようなカルバゾール系化合物、スチルベン、４－ジ－パラ－トリルアミノスチルベンのようなスチルベン系化合物、ＯｘＺのようなオキサゾール系化合物、トリフェニルメタン、ｍ－ＭＴＤＡＴＡのようなトリフェニルメタン系化合物、１－フェニル－３－（パラ－ジメチルアミノフェニル）ピラゾリンのようなピラゾリン系化合物、ベンジン（シクロヘキサジエン）系化合物、トリアゾールのようなトリアゾール系化合物、イミダゾールのようなイミダゾール系化合物、１，３，４－オキサジアゾール、２，５－ジ（４－ジメチルアミノフェニル）－１，３，４－オキサジアゾールのようなオキサジアゾール系化合物、アントラセン、９－（４－ジエチルアミノスチリル）アントラセンのようなアントラセン系化合物、フルオレノン、２，４，７－トリニトロ－９－フルオレノン、２，７－ビス（２－ヒドロキシ－３－（２－クロロフェニルカルバモイル）－１－ナフチルアゾ）フルオレノンのようなフルオレノン系化合物、ポリアニリンのようなアニリン系化合物、シラン系化合物、１，４－ジチオケト－３，６－ジフェニル－ピロロ－（３，４－ｃ）ピロロピロールのようなピロール系化合物、フルオレンのようなフルオレン系化合物、ポルフィリン、金属テトラフェニルポルフィリンのようなポルフィリン系化合物、キナクリドンのようなキナクリドン系化合物、フタロシアニン、銅フタロシアニン、テトラ（ｔ－ブチル）銅フタロシアニン、鉄フタロシアニンのような金属または無金属のフタロシアニン系化合物、銅ナフタロシアニン、バナジルナフタロシアニン、モノクロロガリウムナフタロシアニンのような金属または無金属のナフタロシアニン系化合物、Ｎ，Ｎ’－ジ（ナフタレン－１－イル）－Ｎ，Ｎ’－ジフェニル－ベンジジン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラフェニルベンジジンのようなベンジジン系化合物等が挙げられる。これらは、１種または２種以上を用いることができる。
これらの中でも、α－ＮＰＤ、ＴＰＴＥのようなアリールアミン系化合物が好ましい。
Examples of the p-type low molecular weight material include 1,1-bis (4-di-para-triaminophenyl) cyclohexane and 1,1'-bis (4-di-para-tolylaminophenyl) -4-phenyl. -Arylcycloalkane compounds such as cyclohexane, 4,4', 4''-trimethyltriphenylamine, N, N, N', N'-tetraphenyl-1,1'-biphenyl-4,4'- Diamine, N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD1), N, N'-diphenyl-N, N' -Bis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine (TPD2), N, N, N', N'-tetrakis (4-methoxyphenyl) -1,1'-biphenyl -4,4'-diamine (TPD3), N, N'-di (1-naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (α-NPD), TPTE Arylamine compounds such as N, N, N', N'-tetraphenyl-para-phenylenediamine, N, N, N', N'-tetra (para-trill) -para-phenylenediamine, N, Phenylene diamine compounds such as N, N', N'-tetra (meth-trill) -meth-phenylenediamine (PDA), carbazole compounds, carbazole compounds such as N-isopropylcarbazole, N-phenylcarbazole, Stilben, Stilben compounds such as 4-di-para-tolylaminostylben, oxazole compounds such as OxZ, triphenylmethane, triphenylmethane compounds such as m-MTDATA, 1-phenyl-3- (para-dimethyl). Aminophenyl) Pyrazoline compounds such as pyrazoline, benzine (cyclohexadien) compounds, triazole compounds such as triazole, imidazole compounds such as imidazole, 1,3,4-oxadiazole, 2,5-di Oxaziazole compounds such as (4-dimethylaminophenyl) -1,3,4-oxadiazole, anthracene, anthracene compounds such as 9- (4-diethylaminostyryl) anthracene, fluorenone, 2,4. 7-Trinitro-9-fluorenone, 2,7-bis (2-hydroxy-3- (2-chlorophenylcarbamoyl) -1-naphthylazo) fluorenone compounds such as fluorenone, ani such as polyaniline Phosphorus compounds, silane compounds, 1,4-dithioketo-3,6-diphenyl-pyrrolo- (3,4-c) pyrrol compounds such as pyrrolopyrrole, fluorene compounds such as fluorene, porphyrin, metal tetra Porphyrin compounds such as phenylporphyrin, quinacridone compounds such as quinacridone, phthalocyanine, copper phthalocyanine, tetra (t-butyl) copper phthalocyanine, metallic or non-metal phthalocyanine compounds such as iron phthalocyanine, copper naphthalocyanine, vanadyl. Metallic or metal-free naphthalocyanine compounds such as naphthalocyanine, monochlorogally naphthalocyanine, N, N'-di (naphthalen-1-yl) -N, N'-diphenyl-benzidine, N, N, N', Examples thereof include benzidine compounds such as N'-tetraphenylbenzidine. These can be used alone or in combination of two or more.
Among these, arylamine compounds such as α-NPD and TPTE are preferable.
本発明の有機ＥＬ素子が独立した層として正孔輸送層を有する場合、正孔輸送層の平均厚さは、１０～１５０ｎｍが好ましく、４０～１００ｎｍがより好ましい。
正孔輸送層の平均厚さは、低分子化合物の場合は水晶振動子膜厚計により、高分子化合物の場合は接触式段差計により測定できる。
When the organic EL device of the present invention has a hole transport layer as an independent layer, the average thickness of the hole transport layer is preferably 10 to 150 nm, more preferably 40 to 100 nm.
The average thickness of the hole transport layer can be measured by a crystal oscillator film thickness meter in the case of a small molecule compound and by a contact type step meter in the case of a polymer compound.
（正孔注入層）
正孔注入層の材料としては、酸化バナジウム（Ｖ２Ｏ５）、酸化モリブテン（ＭｏＯ３）、酸化ルテニウム（ＲｕＯ２）等の金属酸化物等が挙げられる。これらは、１種または２種以上を用いることができる。
(Hole injection layer)
Examples of the material of the hole injection layer include metal oxides such as vanadium oxide (V 2 O 5 ), molybdenum oxide (MoO 3 ), and ruthenium oxide (RuO 2 ). These can be used alone or in combination of two or more.
正孔注入層は、酸化バナジウム又は酸化モリブテンを主成分とする層が好ましい。これにより、正孔注入層が陽極から正孔を注入して発光層または正孔輸送層へ輸送する機能がより優れたものとなる。また、酸化バナジウム又は酸化モリブテンは、それ自体の正孔輸送性が高いため、陽極から発光層または正孔輸送層への正孔の注入効率が低下することを防止しやすい。
正孔注入層は、酸化バナジウムおよび酸化モリブテンのいずれか一方または両方からなる層であることがより好ましい。
The hole injection layer is preferably a layer containing vanadium oxide or molybdenum oxide as a main component. This makes the hole injection layer more excellent in the function of injecting holes from the anode and transporting them to the light emitting layer or the hole transport layer. Further, since vanadium oxide or molybdenum oxide has a high hole transport property itself, it is easy to prevent a decrease in the hole injection efficiency from the anode into the light emitting layer or the hole transport layer.
The hole injection layer is more preferably a layer composed of either one or both of vanadium oxide and molybdenum oxide.
正孔注入層には、正孔注入の促進が可能なアクセプター材料である１，４，５，８，９，１２－ヘキサアザトリフェニレン－２，３，６，７，１０，１１－ヘキサカルボニトリル（ＨＡＴ－ＣＮ）、アクセプター材料である２，３，５，６－テトラフルオロ－７，７，８，８－テトラシアノ－キノジメタン（Ｆ４－ＴＣＮＱ）、アクセプター材料であるヘキサフルオロテトラシアノナフトキノジメタン（Ｆ６－ＴＮＡＰ）等を用いてもよい。
In the hole injection layer, 1,4,5,8,9,12-hexazatriphenylene-2,3,6,7,10,11-hexacarbonitrile, which is an acceptor material capable of promoting hole injection, is used. (HAT-CN),
正孔注入層の平均厚さは、１～１０００ｎｍが好ましく、５～５０ｎｍがより好ましい。正孔注入層の平均厚さは、水晶振動子膜厚計により成膜時に測定できる。 The average thickness of the hole injection layer is preferably 1 to 1000 nm, more preferably 5 to 50 nm. The average thickness of the hole injection layer can be measured at the time of film formation with a crystal oscillator film thickness meter.
（製造方法）
本発明の有機ＥＬ素子における各層の形成方法は、特に制限されず、気相成膜法、液相成膜法等から材料に応じて適切な方法を選択できる。層ごとに形成方法が異なっていてもよい。
(Production method)
The method for forming each layer in the organic EL device of the present invention is not particularly limited, and an appropriate method can be selected from a vapor phase film forming method, a liquid phase film forming method, and the like according to the material. The forming method may be different for each layer.
気相成膜法としては、プラズマＣＶＤ、熱ＣＶＤ、レーザーＣＶＤ等の化学蒸着法（ＣＶＤ）、真空蒸着、スパッタリング、イオンプレーティング等の乾式メッキ法、溶射法等が挙げられる。
液相成膜法としては、電解メッキ、浸漬メッキ、無電解メッキ等の湿式メッキ法、ゾル・ゲル法、ＭＯＤ法、スプレー熱分解法、微粒子分散液を用いたドクターブレード法、スピンコート法、インクジェット法、スクリーンプリンティング法等の印刷技術等が挙げられる。
Examples of the vapor deposition method include a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, and laser CVD, a dry plating method such as vacuum vapor deposition, sputtering, and ion plating, and a thermal spraying method.
Liquid phase film forming methods include wet plating methods such as electrolytic plating, dip plating, and electroless plating, sol-gel method, MOD method, spray thermal decomposition method, doctor blade method using fine particle dispersion, and spin coating method. Printing techniques such as the inkjet method and the screen printing method can be mentioned.
化合物（１）を含む電子注入輸送層の形成方法としては、化合物（１）を含む溶液を塗布して形成する方法が好ましい。なお、電子注入輸送層は、真空蒸着法等でも成膜できる。 As a method for forming the electron injection transport layer containing the compound (1), a method of applying a solution containing the compound (1) to form the layer is preferable. The electron injection transport layer can also be formed by a vacuum vapor deposition method or the like.
以上説明したように、本発明の有機ＥＬ素子は、陰極と発光層との間に、環構造ａを含む基と環構造ｂを含む基を有する化合物（１）を含む層を有する逆構造とすることで、優れた駆動安定性を得ることができる。
本発明の有機ＥＬ素子は、材料を適宜選択することによって発光色を変化させることができ、カラーフィルター等を併用して所望の発光色を得ることができるため、表示装置や照明装置の材料として好適に使用できる。
As described above, the organic EL element of the present invention has an inverse structure having a layer containing a compound (1) having a group containing a ring structure a and a group containing a ring structure b between the cathode and the light emitting layer. By doing so, excellent drive stability can be obtained.
The organic EL element of the present invention can change the emission color by appropriately selecting a material, and can obtain a desired emission color by using a color filter or the like in combination, and thus can be used as a material for a display device or a lighting device. Can be suitably used.
なお、本発明の有機ＥＬ素子は、前記した有機ＥＬ素子１，１Ａには限定されない。
陰極、電子注入層、電子輸送層、発光層、正孔輸送層、正孔注入層、陽極の各層は、１層で形成されていてもよく、２層以上からなる層であってもよい。
有機ＥＬ素子における陰極、金属酸化物層、電子注入輸送層、発光層、正孔輸送層、正孔注入層、陽極の各層の間に他の層を有する有機ＥＬ素子であってもよい。他の層としては、例えば、有機ＥＬ素子の特性をさらに向上させる目的で形成される電子阻止層が挙げられる。
The organic EL element of the present invention is not limited to the above-mentioned
Each layer of the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode may be formed of one layer or may be a layer composed of two or more layers.
It may be an organic EL element having another layer between each layer of the cathode, the metal oxide layer, the electron injection transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in the organic EL element. Examples of the other layer include an electron blocking layer formed for the purpose of further improving the characteristics of the organic EL device.
＜表示装置＞
本発明の表示装置は、本発明の有機ＥＬ素子を含む表示装置である。本発明の表示装置は、本発明の有機ＥＬ素子を用いる以外は公知の態様を採用でき、例えば、本発明の有機ＥＬ素子を複数配列した素子配列群を用いて画像を表示する装置が挙げられる。
<Display device>
The display device of the present invention is a display device including the organic EL element of the present invention. The display device of the present invention can adopt known aspects other than using the organic EL element of the present invention, and examples thereof include a device for displaying an image using an element array group in which a plurality of organic EL elements of the present invention are arranged. ..
＜照明装置＞
本発明の照明装置は、本発明の有機ＥＬ素子を含む照明装置である。本発明の照明装置は、本発明の有機ＥＬ素子を用いる以外は公知の態様を採用でき、例えば、本発明の有機ＥＬ素子を複数配列した素子配列群を用いて面発光を行う装置が挙げられる。
<Lighting device>
The lighting device of the present invention is a lighting device including the organic EL element of the present invention. The lighting device of the present invention can adopt a known aspect other than using the organic EL element of the present invention, and examples thereof include a device that performs surface emission using an element array group in which a plurality of the organic EL elements of the present invention are arranged. ..
以下に実施例を掲げて本発明をさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".
［実施例１］
以下に示す方法により、図１に例示した有機ＥＬ素子１を製造した。
ＩＴＯからなる厚み１５０ｎｍのパターニングされた電極（陰極３）が形成されている平均厚さ０．７ｍｍの市販の透明ガラス基板（基板２）を用意し、アセトン中、イソプロパノール中で順に超音波洗浄した後、ＵＶオゾン洗浄を２０分間行った。
亜鉛金属をターゲットとし、反応ガスとして酸素、キャリアガスとしてアルゴンを用いたスパッタ法により、陰極３上に平均厚さ１０ｎｍの酸化亜鉛（ＺｎＯ）層を形成した後、イソプロパノール、アセトンで順次洗浄した。さらに、基板をスピンコーターにセットし、１質量％酢酸マグネシウム溶液（水／エタノール＝１／３）を毎分１６００回転で６０秒スピンコートし、大気下においてホットプレートにより４００℃で１時間アニールを行った。基板を水で洗浄した後、大気下においてホットプレートにより２５０℃で３０分間乾燥させ、陰極３上に金属酸化物層４を形成した。
[Example 1]
The
A commercially available transparent glass substrate (substrate 2) having an average thickness of 0.7 mm on which a patterned electrode (cathode 3) having a thickness of 150 nm made of ITO was formed was prepared and ultrasonically cleaned in acetone and isopropanol in order. After that, UV ozone washing was performed for 20 minutes.
A zinc oxide (ZnO) layer having an average thickness of 10 nm was formed on the
金属酸化物層４まで形成した基板２をスピンコーターに設置し、シクロペンタノンに化合物（１－１）（１質量％）と化合物（２）（ＤＢＮ、２質量％）を溶解した溶液を金属酸化物層４上に滴下しながら、基板２を毎分３０００回転で３０秒間回転させて塗膜を形成した。その後、ホットプレートを用いて窒素雰囲気下で１２０℃、２時間のアニール処理を施し、平均厚さ３０ｎｍの電子注入輸送層５を形成した。
The
電子注入輸送層５まで形成した基板２を、真空蒸着装置の基板ホルダーに固定した。下記式（１１）で示されるビス［２－（２－ベンゾチアゾリル）フェノラト］亜鉛（ＩＩ）（Ｚｎ（ＢＴＺ）２）と、下記式（１２）で示されるトリス［１－フェニルイソキノリン］イリジウム（ＩＩＩ）（Ｉｒ（ｐｉｑ）３）と、下記式（１３）で示されるＮ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニル－１，１’－ビフェニル－４，４’－ジアミン（α－ＮＰＤ）と、下記式（１４）で示されるＮ４，Ｎ４’－ビス（ジベンゾ［ｂ，ｄ］チオフェン－４－イル）－Ｎ４，Ｎ４’－ジフェニルビフェニルー４，４’－ジアミン（ＤＢＴＰＢ）と、Ａｌとを、それぞれアルミナルツボに入れて蒸着源にセットした。
The
真空蒸着装置内を約１×１０－５Ｐａの圧力となるまで減圧し、Ｚｎ（ＢＴＺ）２をホスト、Ｉｒ（ｐｉｑ）３をドーパントとして２０ｎｍ共蒸着し、発光層６を成膜した。このとき、ドープ濃度は、Ｉｒ（ｐｉｑ）３が発光層６全体に対して６質量％となるようにした。
発光層６上にＤＢＴＰＢを１０ｎｍ、α－ＮＰＤを３０ｎｍそれぞれ蒸着し、正孔輸送層７を成膜した。正孔輸送層７上に、三酸化モリブデン（ＭｏＯ３）を真空一貫で蒸着し、平均厚さ１０ｎｍの正孔注入層８を成膜した。正孔注入層８上にＡｌを蒸着し、平均厚さ１００ｎｍの陽極９を成膜し、有機ＥＬ素子を得た。
The pressure inside the vacuum vapor deposition apparatus was reduced to about 1 × 10 -5 Pa, and Zn (BTZ) 2 was used as a host and Ir (piq) 3 was used as a dopant to co-deposit 20 nm to form a
DBTPB was deposited at 10 nm and α-NPD at 30 nm on the
［実施例２～５］
表１に示すように、電子注入輸送層の形成において、化合物（１－１）の代わりに化合物（１－２）～（１－５）を用いた以外は、実施例１と同様にして有機ＥＬ素子を得た。
[Examples 2 to 5]
As shown in Table 1, in the formation of the electron injection transport layer, the compounds (1-2) to (1-5) were used instead of the compound (1-1), but they were organic in the same manner as in Example 1. An EL element was obtained.
［比較例１～５］
表１に示すように、電子注入輸送層の形成において、化合物（１－１）の代わりに化合物（２１）～（２５）を用いた以外は、実施例１と同様にして有機ＥＬ素子を得た。
[Comparative Examples 1 to 5]
As shown in Table 1, an organic EL device was obtained in the same manner as in Example 1 except that compounds (21) to (25) were used instead of compound (1-1) in the formation of the electron injection transport layer. rice field.
［発光特性の測定］
各例で得た有機ＥＬ素子に対して、ケースレー社製の「２４００型ソースメーター」を用いて電圧を印加し、コニカミノルタ社製の「ＬＳ－１００」を用いて輝度を測定した。初期輝度を１０００ｃｄ／ｍ２として連続駆動し、経過時間に対する輝度の変化を調べ、輝度半減寿命（時間）を算出した。結果を表１に示す。
また、実施例１および比較例１、３～５における経過時間に対する輝度の変化をプロットした結果を図３に示す。
[Measurement of emission characteristics]
A voltage was applied to the organic EL element obtained in each example using a "2400 type source meter" manufactured by Keithley, and the brightness was measured using "LS-100" manufactured by Konica Minolta. The initial luminance was set to 1000 cd / m 2 , and the change in luminance with respect to the elapsed time was investigated, and the luminance half life (time) was calculated. The results are shown in Table 1.
Further, FIG. 3 shows the results of plotting the changes in luminance with respect to the elapsed time in Example 1 and Comparative Examples 1 and 3 to 5.
表１および図３に示すように、電子注入輸送層に化合物（１）を用いた実施例１～５の有機ＥＬ素子は、電子注入輸送層に化合物（１）以外の化合物を用いた比較例１～５の有機ＥＬ素子に比べて、輝度が減衰しにくく、長寿命であり、駆動安定性に優れていた。
環構造ａを含む基がビカルバゾール基である実施例４の有機ＥＬ素子は、インドロカルバゾール基である実施例１やベンゾフランカルバゾール基である実施例５の有機ＥＬ素子と同等の長寿命が確保されていた。この結果は、環構造ａを含む基には、環構造ａを含むπ共役系のより大きな環は必ずしも必要ではないことを示している。
As shown in Table 1 and FIG. 3, the organic EL devices of Examples 1 to 5 using the compound (1) in the electron injection transport layer are comparative examples in which a compound other than the compound (1) is used in the electron injection transport layer. Compared with the organic EL elements of 1 to 5, the brightness is less likely to be attenuated, the life is long, and the drive stability is excellent.
The organic EL device of Example 4 in which the group containing the ring structure a is a bicarbazole group has a long life equivalent to that of the organic EL device of Example 1 which is an indolocarbazole group and Example 5 which is a benzofurancarbazole group. It had been. This result indicates that the group containing the ring structure a does not necessarily require a larger ring of the π-conjugated system containing the ring structure a.
比較例４で電子注入輸送層に用いた化合物（２４）は、アクセプター性の基が実施例１で用いた化合物（１－１）と同じトリアジン環（環構造ｂ）を含む基であり、ドナー性の基がトリフェニルアミノ基であり、化合物（１－１）のカルバゾール環（環構造ａ）を含む基とは異なっている。これらの比較から、有機ＥＬ素子の長寿命化には、ドナー性の基として環構造ａを含む基が有効であることがわかる。 The compound (24) used for the electron injection transport layer in Comparative Example 4 is a group containing the same triazine ring (ring structure b) as the compound (1-1) used in Example 1 as an acceptor group, and is a donor. The sex group is a triphenylamino group, which is different from the group containing the carbazole ring (ring structure a) of compound (1-1). From these comparisons, it can be seen that a group containing a ring structure a as a donor group is effective for extending the life of the organic EL device.
比較例１、３で電子注入輸送層に用いた化合物（２１）、（２３）は、ドナー性の基が実施例１で用いた化合物（１－１）と同じインドロカルバゾール基であり、アクセプター性の基がそれぞれシアノ基、ジベンゾオキシド基であり、化合物（１－１）のトリアジン環（環構造ｂ）を含む基とは異なっている。これらの比較から、有機ＥＬ素子の長寿命化には、アクセプター性の基として環構造ｂを含む基が有効であることがわかる。 The compounds (21) and (23) used for the electron injection transport layer in Comparative Examples 1 and 3 have the same donor group as the compound (1-1) used in Example 1 and are acceptors. The sex groups are a cyano group and a dibenzooxide group, respectively, which are different from the group containing the triazine ring (ring structure b) of the compound (1-1). From these comparisons, it can be seen that a group containing a ring structure b as an acceptor group is effective for extending the life of the organic EL device.
アクセプター性の基としてトリアジン環（環構造ｂ）を含む基を有するが、ドナーの基を有しない化合物（２５）を用いた比較例５の有機ＥＬ素子は、素子寿命は極めて短かった。この結果からも、ドナー性の基である環構造ａを含む基と、アクセプター性の基である環構造ｂを含む基を組み合わせた化合物を電子注入輸送層の材料として用いることが、長寿命化に重要であることがわかる。
このように、逆構造の有機ＥＬ素子における電子注入輸送層の材料として化合物（１）が有効であることが確認された。
The organic EL device of Comparative Example 5 using the compound (25) having a group containing a triazine ring (ring structure b) as an acceptor group but not having a donor group had an extremely short device life. From this result as well, it is possible to extend the life of the compound by combining a group containing a ring structure a, which is a donor group, and a group containing a ring structure b, which is an acceptor group, as a material for the electron injection transport layer. It turns out to be important.
As described above, it was confirmed that the compound (1) is effective as a material for the electron injection transport layer in the organic EL device having the reverse structure.
［分子軌道（ＨＯＭＯ軌道／ＬＵＭＯ軌道）の分布］
分子軌道計算ソフトGaussian09を用いて、化合物（１－１）、化合物（２１）、化合物（２３）、化合物（２４）および化合物（２５）のＨＯＭＯ（最高被占軌道）－ＬＵＭＯ（最低空軌道）の分子軌道計算を行った。結果を図４～８に示す。
[Distribution of molecular orbitals (HOMO orbitals / LUMO orbitals)]
HOMO (highest occupied molecular orbital) -LUMO (lowest unoccupied molecular orbital) of compound (1-1), compound (21), compound (23), compound (24) and compound (25) using the molecular orbital calculation software Gaussian09. Molecular orbital calculation was performed. The results are shown in FIGS. 4-8.
図８に示すように、アクセプター性の基（トリアジン基）は有するが、ドナー性の基を有しない化合物（２５）では、ＨＯＭＯとＬＵＭＯの両方がトリアジン基に偏在していた。これに対して、図４～７に示すように、ドナー性の基とアクセプター性の基の両方を有する化合物（１－１）、化合物（２１）、化合物（２３）、化合物（２４）では、ＬＵＭＯはアクセプター性の基付近に偏在し、ＨＯＭＯはドナー性の基付近に偏在していた。このように、ドナー性の基とアクセプター性の基を組み合わせた化合物では、分子内でＨＯＭＯ／ＬＵＭＯの軌道が分離していた。 As shown in FIG. 8, in the compound (25) having an acceptor group (triazine group) but not a donor group, both HOMO and LUMO were unevenly distributed in the triazine group. On the other hand, as shown in FIGS. 4 to 7, in the compound (1-1), the compound (21), the compound (23), and the compound (24) having both a donor group and an acceptor group, LUMO was unevenly distributed near the acceptor group, and HOMO was unevenly distributed near the donor group. As described above, in the compound in which the donor group and the acceptor group are combined, the HOMO / LUMO orbitals are separated in the molecule.
アルカリ金属等を電子注入層に用いない逆構造の有機ＥＬ素子においては、電子の注入に比べて正孔の注入が容易になるため、多くの正孔が電子注入輸送層まで到達する。素子寿命が極めて短い比較例５は、化合物（２５）がアクセプター性の基のみを有する材料であり、正孔の影響を受けるＨＯＭＯがアクセプター性の基に局在しているため、正孔に対する耐性が低く、劣化しやすいと考えられる。実施例１や比較例１、３、４が比較例５に比べて素子の安定性が高いのは、化合物（１－１）、化合物（２１）、化合物（２３）、化合物（２４）においてＬＵＭＯとＨＯＭＯが分子内で分離し、ＨＯＭＯがアクセプター性の基に局在しておらず、化合物（２５）に比べて正孔に対する耐性が高くなるためであると考えられる。 In an organic EL element having a reverse structure in which an alkali metal or the like is not used for the electron injection layer, holes are easily injected as compared with electron injection, so that many holes reach the electron injection transport layer. Comparative Example 5, which has an extremely short device life, is a material in which compound (25) has only an acceptor-like group, and HOMO affected by holes is localized in the acceptor-like group, so that it is resistant to holes. Is low and is considered to be prone to deterioration. The elements of Example 1 and Comparative Examples 1, 3 and 4 are more stable than those of Comparative Example 5 in the LUMO of the compound (1-1), the compound (21), the compound (23) and the compound (24). It is considered that this is because HOMO and HOMO are separated in the molecule, HOMO is not localized in the acceptor-like group, and the resistance to holes is higher than that of compound (25).
また、化合物（１－１）、化合物（２１）、化合物（２３）、化合物（２４）は同様にＬＵＭＯとＨＯＭＯが分子内で分離しているが、化合物（１－１）は化合物（２１）、化合物（２３）、化合物（２４）に比べて長寿命化効果が特に優れている。そのため、化合物（１）による有機ＥＬ素子の長寿命化には、ＬＵＭＯとＨＯＭＯが分子内で分離するだけでなく、ドナー性の基とアクセプター性の基として、環構造ａを含む基と環構造ｂを含む基という特定の基の組み合わせが重要である。 Further, in the compound (1-1), the compound (21), the compound (23), and the compound (24), LUMO and HOMO are similarly separated in the molecule, but the compound (1-1) is the compound (21). , The effect of extending the service life is particularly excellent as compared with the compound (23) and the compound (24). Therefore, in order to extend the life of the organic EL device by the compound (1), not only LUMO and HOMO are separated in the molecule, but also a group containing a ring structure a and a ring structure as donor and acceptor groups are used. The combination of specific groups, the groups containing b, is important.
１，１Ａ…有機ＥＬ素子、２…基板、３…陰極、４…金属酸化物層、５…電子注入輸送層、６…発光層、７…正孔輸送層、８…正孔注入層、９…陽極。 1,1A ... Organic EL element, 2 ... Substrate, 3 ... Cathode, 4 ... Metal oxide layer, 5 ... Electron injection transport layer, 6 ... Light emitting layer, 7 ... Hole transport layer, 8 ... Hole injection layer, 9 …anode.
Claims (4)
前記陰極と前記発光層の間に、下記式（ａ）で示される環構造を含む基と下記式（ｂ）で示される環構造を含む基とを有する化合物を含む層を有し、
前記層が、酸解離定数ｐＫａが１以上である塩基性の化合物をさらに含み、
前記層と前記陰極との間に金属酸化物層を有することを特徴とする、有機エレクトロルミネッセンス素子。
A layer containing a compound having a group having a ring structure represented by the following formula (a) and a group having a ring structure represented by the following formula (b) is provided between the cathode and the light emitting layer .
The layer further comprises a basic compound having an acid dissociation constant pKa of 1 or greater.
An organic electroluminescence device characterized by having a metal oxide layer between the layer and the cathode .
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| JP2014049697A (en) | 2012-09-03 | 2014-03-17 | Nippon Hoso Kyokai <Nhk> | Organic electroluminescent element |
| CN104183763A (en) | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Inverted organic light emission diode and preparation method and application thereof |
| JP2016054027A (en) | 2014-09-02 | 2016-04-14 | 日本放送協会 | Organic electroluminescent element |
| WO2016181705A1 (en) | 2015-05-11 | 2016-11-17 | 日本放送協会 | Organic thin film and method for manufacturing organic thin film, organic electroluminescence element, display device, illumination device, organic thin film solar cell, thin film transistor, and coating composition |
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| CN104183763A (en) | 2013-05-22 | 2014-12-03 | 海洋王照明科技股份有限公司 | Inverted organic light emission diode and preparation method and application thereof |
| JP2016054027A (en) | 2014-09-02 | 2016-04-14 | 日本放送協会 | Organic electroluminescent element |
| JP2017531309A (en) | 2014-10-01 | 2017-10-19 | エルジー・ケム・リミテッド | Organic light emitting device |
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